FR2648821A1 - - Google Patents

Abstract

The present invention relates to organofunctional polydiorganosiloxanes with an amino and polyoxyalkylene function of the formula: (CF DRAWING IN BOPI) The polymers of formula 1 are prepared in two or three stages involving a hydrosilylation reaction. The polymers of formula 1 can be used in particular as surfactant, dispersing agent, silicone additive to a softening composition for rinsing textiles or to a solid antifoam for powder detergent.

Description

ORGANO-FUNCTIONAL FUNCTIONAL PCLYDIORGANOSILOXANES

AMINO AND POLYOXYALKYLENE

  The present invention relates to organofunctional polydiorganosiloxanes having an amino function and polyoxyalkylene, their methods of

preparation and their applications.

  The literature describes a very large number of polydiorganosiloxanes with amino function or polyoxyalkylene function and their various uses in particular in detergent compositions, defoamers, polyurethane foam additives, compositions

polish. etc .....

  GB-A-1,409,741 and GB-A-1,409,742 describe the synthesis of aminofunctional polydiorganosiloxanes having alkoxy groups. These products are prepared by partial reaction of allylamine with a polydiorganosiloxane carrying SiH hydride function in the presence of a platinum catalyst. The residual E SiH are then reacted with an alcohol, for example isopropanol. These products are used as

  detergent resistant polishing additives.

  US-A-4 184 004 discloses an epoxy functional polydiorganosiloxane and

  has polyoxyalkylene function and its use as a fabric softener.

  GB-A-2,201,433 discloses the use of a polyoxyalkylene functional ammonium polydiorganosiloxane as an additive to a

  detergent or rinse composition.

  EP-A-58 493 relates to the use of the combination of three functional polydiorganosiloxanes (A), (B) and (C), for the treatment of textile fibers, (A) comprising both amino groups and groups polyoxyalkylene. Although the definition given to (A) is extremely broad, EP-A-58 493 specifically discloses only a particular oil A of the formula: Me (Me 2 SiO) 130 (MeFSiO) 3 (MeGSiO) 10SiMe 3, with F = - ( CH2) 3 -NH (CH2) 2MH2

G = - (CH2) 30 (C2H40) 10H

  It is an object of the present invention to provide an amine and polyoxyalkylene functional polydiorganosiloxane of easy manufacture. Another object of the present invention is to provide a polydiorganosiloxane of the above type, stable in an aqueous medium, having a hydrophilic character that can be easily emulsified or microemulsion and can be, in some cases water soluble or

  dispersible in aqueous media.

  Another object of the present invention is to provide a polydiorganosiloxane of the above type which can be used as a surfactant and as an additive in detergent compositions and in particular in laundry rinse compositions and as an additive in

an antifoam silicone.

  These and other objects are achieved by the present invention which in fact relates to a polydiorganosiloxane having an amino and polyoxyalkylene function of average formula: R 3 SiO (R SiO) m (R SiO) (RSiO) (R2SiO) qSiR3 n p

(CH2) 3 (CH2) 3 OR "

1 (1) X Y - (OC 2H 4) a (OC 3 H 6) b OR 'I

NH2

  in which: R is chosen from C 1 -C 4 alkyl, phenyl and 3,3,3-trifluoropropyl radicals, at least 80% by number of R radicals being methyl radicals, X is chosen from a single covalent bond and the divalent radical of formula:

  - O - CH2 - CH (OH) - CH2 - NH - W - (2)

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  Y is chosen from a single covalent bond and the divalent radical of formula:

CHI - CH - CH2OCH3 (3)

  With the proviso that if p = 0 and X is a covalent bond, Y is the radical of formula (3), m is 1 to 25, preferably 1 to 10, n is 1 to 25, preferably 1 at 10, p varies from 0 to 15, preferably from 1 to 5, q ranges from 5 to 500, preferably from 10 to 400, a varies from 0 to 150, b varies from 0 to 150, a + b varies from 5 to at 200, W is a divalent hydrocarbon radical having 1 to 6 carbon atoms such that - CH2 -, (CH2) 2-, -r'2) 3, - (CH2) 6-, - (CH2) - is the preferred radical, R 'is chosen from a hydrogen atom, a C1-C6 alkyl radical, a C1-C6 acyl radical and a phenyl radical, R' is preferably methyl, as is the radical R, R " is a linear or branched C1-C6 alkyl radical, preferably

isopropyl and isobutyl.

  By varying in particular the ratio a / b and the sum a + b, it is possible to easily modify the hydrophilic nature and the character

  hydrophobic polymers of formula (1).

  The polymers of formula (1), in the case where X is a covalent bond and Y the divalent radical of formula (3), can advantageously be prepared as follows:

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  The starting material is a hydrogenopolydiorganosiloxane of formula: ## STR3 ## wherein R and q have the meaning given above and

c = m + n + p.

  During a first step, the SiH functions of the polymer (4) are partially hydrosilylated by adding a suitable amount of allylamine in the presence of a hydrosilylation catalyst, preferably a catalyst.

1C platinum.

  The platinum catalysts used to carry out the hydrosllylation reaction of the polymers of formula (4) are amply described in the literature, mention may in particular be made of platinum complexes and of an organic product described in US Pat. 3,159,601, US-A-3,159,602, US-A-3,220,972 and European Patents EP-A-57,459, EP-A-188,978 and EPA-A-190,530, and platinum and organopolysiloxane vinyl described in US Patents

  US-A-23 41.9 593, US-A-3,737,432 and US-A-3,814,730.

  In order to react the polymer of formula (4) with allylamine, a quantity of platinum catalyst calculated as the weight of platinum metal of between 5 and 600 ppm is preferably used, preferably between 10 and 10 ppm.

  and 200 ppm based on the weight of SiH polymer of formula (4).

  The hydrosilylation reaction can take place in bulk or in a volatile organic solvent such as toluene, heptane, xylene,

  tetrahydrofuran, tetrachlorethylene and white spirit.

  It is generally desirable to heat the reaction mixture to a temperature between 30 and 200 C for the time necessary for the reaction to be complete. Furthermore it is desirable to add dropwise the allylamine to the polymer of formula (4) in solution in an organic solvent and, preferably to

reflux temperature of the solvent.

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  Then the solvent is optionally removed for example by distillation under reduced pressure. However the polymer solution

  obtained can be directly used for the second step of the process.

  The polymer obtained has the formula: PR3SiO (RSiO) m (RHSiO) d (R2SiO) qSiR3 (5)

(CH2) 3

  NH2 P. m and q having the meaning given above and d = n - p. The polymer of formula (5) may contain, as impurities, a small amount of formula unit:

CH - Si - O -

NH CHI CH = CH2 and

! I

R - Si CH 2 CH 2 CH 2 NH - Si - R

I

O o

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  4- During a second gold step. hydrosilyl all or part of the functions - SiH reslduelles the polymer of formula (5) with an unsaturated polyoxyalkylene of formula: Cs CH2 = CHCH2OCH2CH CH2OCH (6) TO (OC2H4) a (OC3H6) b - OR'P

  at. b and R 'having the same meaning as above.

  This second step is analogous to the first step. It is preferably carried out in an organic solvent medium, preferably the same as that used in the first step and then starting from the polymer solution (5) obtained at the end of the first step. It is not necessary to add a platinum catalyst which is already contained in

this solution.

  The solvent is removed for example by distillation under reduced pressure. The polymer obtained can be purified, for example by passing over

an absorbent column of silica.

  If this polymer does not contain residual SiH functions, it corresponds to formula (1) with p = 0. If this polymer contains residual E SiH, they are reacted with an alcohol of formula R "OH, R" having the meaning given above, in the presence of a catalyst such as diethylhydroxylamine according to the teaching of GB-A-1 409 741 and

GB-A-1,409,742 cited above.

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  Of course, it can remain in the polymer of formula (1). as impurities. Formula patterns:

CH, = - Si - O -

  CH 2 CH 2 CH = CH and R - Si CH 2 CH 2 CH 2 NH - Si - R

2 2

C O

  These units can be blocked by reaction with an alcohol of formula R "OH giving units of formulas: RSiO and RSiO

OR "(CH2) 3NH2.

  To prepare the polymers of formula (1) for which X is a radical of formula (2), starting from a polymer of formula (4) as defined above, in which, during a first step, a reaction is carried out. partial hydrosilylation by means of an unsaturated polyokyalkylene of formula: ## STR5 ## wherein Y, a, b and R 'have the meaning given above to obtain the polymer of formula:

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  e-RS10O (RHSiC) RSiO) n (R2510q SiR (8) I

(CH 2) 3

  Wherein R, R ', Y, x, q, a and b have the meaning given above and e = m + p. of formula (8) is hydrosilylated completely with allylglycidyl ether of formula:

CH = CHCH2OCH2CH CH

  The polymer obtained, which can be prepared according to the teaching of US-A4 184 004 mentioned above, is optionally reacted with an alcohol R "OH in the case where residual E SiH remains. reaction with a molar excess of a diamine of formula H, N WNH ,, W having the meaning given above and thus obtaining the

polymer of formula (1).

  The polymer of formula (1) is substantially linear being

  practically only patterns M: (R3SiO) and D: (R2SiO).

  However, up to 10 mol% of T: (RSiO3 / 2) units can

to be present.

  The polymer of formula (1) may be water-soluble, dispersible in water or insoluble in cold or hot water. Generally the solubility in water is increased by increasing the weight content of polyoxyalkylene groups in the polymer and by varying the ratio

a / b and the sum a + b.

  The polymer of formula (1) can therefore, as the case may be, be used as such, in solution in an organic solvent, in solution or in

  aqueous dispersion, emulsion and microemulsion.

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  The polymers according to the invention can be used in particular for treating glass fibers and organic fibers (sizes), textile treatment and softening, as tenso-active agents, water-repellent agents, release agents, lubricants, additives for organic polymers, in particular PVC. , lubricants for textile fibers, additive

  for polish resistant to detergents. antifoaming and defoaming agents.

  The polymers of formula (1) are particularly useful in mass or in solution in an organic solvent for treating textile fibers. They are then preferably used in combination with an oil, t (dihydroxy) polydiorganosiloxane with a viscosity of between 100 and 150,000 mPa.s at 25 ° C., the organic radical of which is preferably methyl, optionally in the presence of a condensation catalyst such as

than a tin salt.

  It is then used for 100 parts of polymer (1), 10

1000 parts of hydroxylated oil.

  The polymers according to the invention are more particularly useful on the one hand as dispersing agents in solid defoamers for washing powders and, on the other hand, as a silicone additive in textile rinsing compositions with or without a surfactant.

  organic, preferably catlonic.

  The solid antifoam for washing powder comprises: 100 parts of a matrix chosen by a polyethylene glycol, a polyoxyethylene / polyoxypropylene copolymer, a solid surfactant such as a mono- or tri-stearate sorbitan and a solid wax, and their various mixtures possible, - 10 to 80 parts of a dispersion of pyrogenation silica or of precipitation in a silicone oil, generally a polydimethylsiloxane oil,

  - 1 to 20 parts of polymer of formula (1).

  This antifoam is prepared in the following manner: the silica / polydimethylsiloxane dispersion is hot-mixed in a molten matrix which is either soluble or insoluble or dispersible in water by adding the dispersing agent which is the polymer of formula (1) according to the invention.

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  Then the molten dispersion is cooled, then the mass is ground.

  resulting solid to obtain a powder flowing well.

  According to the second application, more specifically targeted, the polymer of formula (1) is utllise as a silicone additive in a rinsing composition, comprising an aqueous dispersion of at least one cationic organic surfactant, substantive to textiles and softening textiles, as described in FR-A-2,318,268, cited as a reference, which is generally a quaternary ammonium salt having two radicals

  long chain alkyl, generally C 12 -C 2.

  1C At least one polymer of formula (1) is added as appropriate to the cationic surfactant in the form of an emulsion, a dispersion or an aqueous solution. The weight ratio of the organic surfactant to

  the polymer (1) is between 3/1 and 1/20.

  The rinsing bath is then effective at an organic surfactant content, more polymer of formula (1) between 15 and

  600 ppm, of which at least 8 ppm of polymer of formula (1).

  In all of the following or the foregoing, unless otherwise indicated

  In contrast, the parts and percentages given are by weight.

  The following examples illustrate the invention without limiting its

scope.

EXAMPLE 1

  114.4 parts of a hydrogenopolydimethylsiloxane of average formula Me3SiO (Me2SiC) (MeHSiO) 3SiMe (Me = CH3), 100 parts of toluene and 0.016 part of platinum chloride of bis (diethylsulphide) are heated under reflux. to remove all the water, 5 parts of allylamine are added dropwise during

an hour to reflux.

  The reflux is continued for another 45 minutes.

  A sample of the reaction mixture is then taken and has a neutralization equivalent of 1554 and an infra-red spectrum.

  demonstrating the presence of E SiH group.

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  136 parts of the poly (oxyalkylene) of average formula are then added to the reaction mixture:

CH = CH CH2 OCH2 CH CH2 OCH3

OS22 3

bone

(OCH2CH2) 10 - {OCH2CH (CH3)} 07 - OH

  obtained by reaction of suitable amounts of ethylene oxide and

  propylene on allylglycidylether in the presence of sodium methalonate.

  This addition is made under reflux for 50 minutes and the reaction mixture is heated under reflux for a further

1 hour 30 minutes.

  The solvent is removed under vacuum at 100 [deg.] C. and a yellow oil with a viscosity of 100 mPa.s at 25 ° C. is thus obtained. This oil contains no residual SiH groups and has a neutralization equivalent of 3,480. The oil is dispersible in water and has a cloudy point of

53 C.

EXAMPLE 2

  142 parts of hydrogenopolydimethylsiloxane of average formula: MeSiO (Me2SiO) 15 (MeHSiO) 3SiMe3, 100 parts of toluene and 0.022 part of platinum chloride of bis (diethylsulfide) are mixed and refluxed, 3 parts of allylamine are added dropwise during

reflux minutes.

  A sample of the reaction mixture is then taken. After removal of the solvent, this sample has an equivalent

neutralization of 2,852.

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  The IR spectrum demonstrates the presence of residual - SiH groups.

  - 195 parts of the polyoxyalkylene used in Example 1 are

added at reflux for 5 minutes.

  A cloudy solution is obtained which becomes clear after a

reflux of 2 hours 30 minutes.

  At the end of this period, all the residual groups E SiH disappeared. After removal of toluene, an oil with a viscosity of 380 mPa.s

  aC is obtained having a neutralization equivalent of 7,400.

  This oil is dispersible in water with a cloud point of

59 C.

EXAMPLE 3

  The exact procedure of Example 1 is repeated except that: - 144.8 parts of a hydrogenopydimethylsiloxane oil of average formula: Me3SiO (Me2SiO) 14 (MeHSiO) 4SiMe3, - 100 parts of toluene, - 3 parts of allyamine and

  0.016 parts of the same platinum catalyst.

  -C The sampled sample has a neutralization equivalent of

2,900.

  270 parts of the same polyoxyalkylene are added to finally obtain an oil of viscosity 302 mPa.s at 25 ° C., an equivalent

  neutralization of 9 100 and a cloud point of 52 C.

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EXAMPLE 4

  The procedure of Example 1 is repeated exactly, except that: - 477.8 parts of a hydrogenopydimethylsiloxane of average formula O5: Me3SiO (Me2SiO) 15 (MeHSO) 3 1SiMe3, - 400 parts of toluene and 0.0594 parts of the same platinum catalyst and 19.95 parts of allylamine followed by the addition of

  577 parts of the same polyoxyalkylene.

  The oil obtained has a viscosity of 165 mPa.s at 25 C, a neutralization equivalent of 3,390 and a cloud point of 52 C:

EXAMPLE 5

  A dispersion is prepared in a kneader by mixing: 95 parts of a trimethylsiloxy-blocked polydimethylsiloxane oil and 5 parts of a hydrophobic silica DEGUSSA SIPERNAT D10,

  marketed by DEGUSSA.

  40 parts of this dispersion are then mixed in the molten state with 55 parts of polyethylene glycol of molecular weight 6000 and parts of the silicone oil obtained in Example 1. The mixture obtained is rapidly cooled, by spreading. in one

  thin film of thickness.

  This film is ground into a rather coarse powder, very

fluid, flowing well.

  The powder consists of grains of the silicone / silica oil dispersion, microencapsulated by a solid matrix of polyethylene glycol which disperses easily in an aqueous medium, giving a very high

good antifoam.

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COMPARATIVE EXAMPLE 6

  CrOn exactly repeats the operating mode of example 5 except that

  the oil of example i is not introduced.

  The solid product obtained is sticky and can not be ground into a

bone powder flowing well.

EXAMPLE 7

  The procedure of Example 5 is exactly repeated except that instead of polyethylene glycol the same amount of sodium stearate is used.

  sorbitan SPAN 65, marketed by the company ICI.

  After grinding, a well-flowing powder is obtained which disperses easily in hot and cold water and is

effective antifoam.

EXAMPLE 8

  The foam height profile is established as a function of the time and temperature of a commercial detergent powder for an automatic washing machine without antifoam, by means of a washing machine

  ZANUSSI FL811 laundry has front opening.

  The same profile is established after incorporation of 0.2% of oil of Example 1. A significant decrease in the level of foam is observed in

  particularly at the end of the high temperature / high agitation washing cycle.

EXAMPLE 9

  162.05 g of a hydrogenopolydimethylsiloxane of average formula: Me3SiO (Me2SiO) 8 (MeHSiO) 3 1SiMe3 are dried by refluxing in toluene for 90 minutes. 42 ppm (calculated on the weight of the silicone oil) of the platinum catalyst used in Example 1 and then 9.98 g of added allylamine are added.

drip for 1 hour.

BAD ORIGINAL

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  The reaction mixture is refluxed for another hour and a sample is taken. This sample, where toluene is removed, requires 13.05 ml of N hydrochloric acid for neutralization. 256.4 g of a polyoxyoloxylene of formula:

CH = CH CH CHCHCHOCH

(OCH2CH2) 8 5- {OCH2CH (CH3!} 5-O

  at reflux for 30 minutes, the solvent being then removed at reflux for 2 hours. The residual - SiH content is 28% of the initial content. The reflux is continued for a further 2 hours to reach a residual content of 19% - SiH. The reaction mixture is cooled to 110 ° C. and 42 ppm platinum catalyst is added. We

  heated and refluxed again for 2 hours.

  The residual SiH content is 8%.

  Refluxing for 3 hours 30 minutes eliminates all

residual = SiH.

  The reaction mixture is cooled to 80 ° C.

  2 g of bentonite, 2 g of activated charcoal and 2 g of water are added while stirring for 90 minutes. We filter on CELITE and we eliminate

solvent under reflux.

  An oil having the following characteristics is obtained: - residual% E SiH: O - equivalent in amine: 3040 - viscosity at 25 C: 172 mPa.s - cloud point: 49 C

  (cloudy solution at 15 C which is completely clear at 25 C).

BAD ORIGINAL

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  m varies from 25, preferably from 1 to 10, n ranges from 1 to 25, preferably from 1 to 10, p varies from 0 to 15, preferably from 1 to 5, q ranges from 5 to 500, preferably from 10 to 400, a varies from 0 to 150, b varies from 0 to 150, a + b varies from 5 to 200,

  W is a divalent hydrocarbon radical having 1 to 6 carbon atoms.

  R 'is chosen from a hydrogen atom, a C1-C6 alkyl radical, a C1-C6 acyl radical and a phenyl radical,

  R "is a linear or branched C1-C6 alkyl radical.

  2. - Polydiorganosiloxane according to claim 1, characterized

  in that R and R 'represent the methyl radical and W is - (CH22-.

  3. - Process for preparing a polydiorganosiloxane as defined in claim 1 or 2 and for which X is a single covalent bond, characterized in that during a first stage orn performs the partial hydrosilylation of a corresponding hydrogenopolydiorganosiloxane by allylamine then in a second step, the hydrosilylation of all or part of the residual E SiH groups is carried out with a polyoxyalkylene of formula:

CH2 = CHCH2OCH2CH CH2OCH3 (6)

(OC2H4) (OC3H6) - OR '

  in which R ', a and b have the meaning given above, then react any residual E SiH groups on the alcohol of formula

  R "OH, R" having the meaning given above.

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- the -

  4. - Process for preparing a polydiorganosiloxane as defined in claim 1 or 2 and for which X is the divaren radical, of formula:

  - O - CH2 - CH (OH) - CH2 - NH - (CH2) 2-

  characterized in that during a first step the corresponding hydrogenopolydiorganosiloxane is hydrosilylated by a polyoxyalkylene of the formula: ## STR2 ## wherein Y, R ', a and b have the meaning given above, during a second step, all or some of the residual SiH groups are hydrosilylated by allylglycidylether, any residual SiH groups are reacted with an alcohol of formula R "OH and During a third step, a diamine of formula H 2 NRH 2 R 2 and R 2 is reacted.

  having the meaning given above.

  5. - Antifoam solid for washing powder, characterized in that it comprises: - 100GO parts by weight of a matrix selected from a polyethylene glycol, a polyoxyethylene / polyoxypropylmene copolymer, a solid surfactant and a solid wax and their various possible mixtures, - 10 to 80 parts of a dispersion of pyrogenation silica or of precipitation in a silicone oil, - 10 to 20 parts of a polymer of formula (2) as defined in

claim 1 or 2.

  6. - solid antifoam according to claim 5, characterized in

  that the solid surfactant is a mono- or tri-stearrate sorbitan.

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  7. - Textile rinse composition comprising: - an aqueous dispersion of at least one surfactant orgarilque cationic * substantive textile, - eemulsicn. a dispersion or an aqueous solution of at least one

  polymer of formula (I) as defined in claims 1 or 2, the

  weight ratio of the organic surfactant to the polymer of

  formula (1) being between 3/1 and 1/20.

  8. - Use for the textile treatment of a polymer of

  formula (1) as defined in claims 1 or 2, in bulk, in

  aqueous dispersion, dissolved in an organic solvent and optionally

  in combination with an α, - (dihydroxy) polydiorganosiloxane.

BAD ORIGINAL p